New HC-110 Formula

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Wallendo

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Short of someone with access to a Tardis who can store a bottle in a safe place and then retrieve it from 10 years from now and bring it back and develop a roll of film, we will know know how long this lasts for a long time.

For me, it was nice to know that HC-110 lasted a long time, but in practice, I like to use all my developers within a 1-2 year period (except for a few bottles of open Rodinal I am saving for future generations.
 

Alan Johnson

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There are no facts from the manufacturer re shelf life and anti-fog performance for the new version vs the old version which, being introduced in 1962,is well documented.
The only facts so far appear to be their MSDS:
https://www.photrio.com/forum/threads/new-hc-110-formula.169322/page-2#post-2202911
If someone can name a solvent other than water capable of dissolving 10-20 % potassium sulfite there might be something to debate.
 

alanrockwood

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I am attaching composition information for the old HC-110, taken from an MSDS dated 2016, and the new HC-110, taken from an MSDS dated 2019: First the old and then the new.

old HC-110 composition information.JPG




new HC-110 composition information.JPG



There are several things we can glean from these. The first is that, regardless of whether they are functionally similar, they are very different formulations. I will return to that point later.

Note the hydroquinone percentages. They are given as ranges due to trade secret issues. However, note that one MSDS lists it as 5-10% and the other lists it as 10-20%. Those two ranges intersect at 10%, so it's a pretty good bet that it is 10% hydroquinone for both formulations. That's not a sure thing however.

The second thing to note is that the sulfite or sulfite equivalent concentrations are very different. The old formulation lists 15-20% sulfur dioxide. (Note that sulfur dioxide becomes sulfurous acid when the developer is mixed with water, which in turn becomes sulfite in basic solution.) The new formula lists potassium sulfite as 10-20%. (I'm ignoring the "<" sign because it is probably meaningless in this situation.) Considering the difference in molecular weight of SO2 and K2SO3, the equivalent sulfite concentration in the old formula is at least 1.84 times higher in the old formula compared to the new formula, and the factor could be as much as 4.94X.

Next, note that, as pointed out by Alan Johnson, the fact that the new formulation contains a high amount of potassium sulfite implies that the formula almost certainly has a high water composition. Otherwise the K2SO3 wouldn't dissolve in the concentrate, unless there is something that can sequester the ions in such a way as to make them soluble in non-aqueous solvents. It's possible that the diethylene glycol might serve this purpose, at least for potassium ions, due to the structural similarity of diethylene glycol to crown ethers, but I doubt if diethylene glycol is a strong enough complexing agent with potassium to make this possible. In any case, that still leaves the problem of solubilizing the doubly charged sulfite ions into a non-aqueous solution. The fact that non-aqueous liquids are only a small part of the new formulation also suggests that there is a lot of water, although non-toxic liquids like propylene glycol might be present and not listed(?) in the msds, so this it is not definitively proven that the formula contains a lot of water.

Note that 1,2 Benzenediol is listed in both sheets. That's catechol, which is a developer. However, my guess is that it is not included for any functional reason, but is probably a side product in the synthesis of hydroquinone, and it's not worth it to try to purify it out because it doesn't harm the function of the developer.

Diethylenetriaminepetnaacetic acid is listed in the old formula. That compound is usually used to complex metal ions in most applications. I can't guess why it's in the old formula (unless it's to help condition dilution-water that contains a lot of iron or some-such), or why it's not in the new formula.

The old formula contains potassium bromide (although I don't know how they manage to keep that in solution), but the new formula does not. Since potassium bromide is a restrainer, it makes you wonder what restrainer they are using in the new formula and also whether the new formula is a low-fog developer like the old formula.

Anyway, the formulations are quite different, and even though they are said to work similarly to each other under normal conditions does not mean they are likely to work similarly under more extreme conditions.

And of course there is that nagging question of shelf life. If I had to bet the farm my guess would be that the shelf life of the new formula is probably only a fraction of that of the old formula, and if so it is a very significant difference for some of us.
 
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Donald Qualls

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nothing to stop anyone making a PQ substitution on those (or Ascorbate) and replacing the borates with newer buffering.

That sounds a lot like a description of the new Adox XT-3 (Xtol replacement).
 

Lachlan Young

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@michael_r Just to add further confusion, there was a partially pre-diluted HC-110 variant sold in UK/ EUR (and elsewhere?) at least into the early 2000's that further diluted 1+9 for dilution 'B'.

@Donald Qualls DK-50/ DK-60a etc are fairly significantly different in behaviour from D-76 - and XT-3 derives from D-76/ Xtol. All I was pointing out is that there are now alternative buffers to borates - and XT-3 uses them.
 

Donald Qualls

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Yes. XT-3 is borate free, according to Adox. So is HC-110, as far as I know. A PC version of HC-110 isn't far from Gainer's PC-TEA (which is cheap to make, keeps almost forever in concentrate form, but has less solvency than HC-110).
 

MattKing

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I wonder if any of the older MSDS relate to working solutions, rather than the concentrate.
On the issue of whether there is any water in the new HC-110: one indicative but certainly not determinative test would be to check whether the concentrate will develop film. The old stuff wouldn't, until you added some water.
 

YoIaMoNwater

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The new formulation has been on sale for over a year. We must have someone by now confirming that a bottle lasts at least a year after opening. Anyone? One year life span would be pretty good. Negative reviews on B&H suggest the new formula goes bad after a "few months", not sure how trustworthy those are, or if people are just repeating what they had read online.
Can’t believe no one else has posted this. I opened this bottle on February 8th this year as a second developer for B&W reversal and it still works. Although it appears a bit darker and more orange than the initial yellow, but when it is diluted I see no differences to fresh HC-110.

This is the UK/Europe one so not sure how it compares to the US one.

4FDDD34B-F762-49B9-B616-C6528493860A.jpeg F625615E-990C-49EE-AFCE-970CA041F3C4.jpeg
 

MattKing

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Can’t believe no one else has posted this. I opened this bottle on February 8th this year as a second developer for B&W reversal and it still works. Although it appears a bit darker and more orange than the initial yellow, but when it is diluted I see no differences to fresh HC-110.

This is the UK/Europe one so not sure how it compares to the US one.

View attachment 282697 View attachment 282698
That probably says Made in Germany on the label, and is the old version of HC-110. They aren't making that version any more.
 

YoIaMoNwater

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MattKing

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Every one of those ads is using the same image, from a bottle with a best before date in 2018 :D.
They, like your bottle, have the old, pre July 30, 2019 Catalog number of 5010541. Since July 2019 the Catalog number is 1058692.
What is the best before date on your bottle? Where does it say it was made?
Here is what the current as of late 2019, Made in the USA version looks like:
1564414830_1493206.jpg
 

alanrockwood

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I have a thought. How about if we develop (do you like the play on words "develop"?) a database of msds datasheets for HC-110, sorted by date of publication. If they are all in one place it could make it easier to discuss the issue of HC-110 composition and changes in composition.
 

MattKing

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Here is a comparison between the Canadian SDS and the Australian - both have a revision date of January 4, 2021 and are submitted by the local Sino Promise subsidiary:
Canada:
upload_2021-8-13_13-25-15.png

Australia:
upload_2021-8-13_13-26-47.png


And finally, here is the UK version, submitted by Sino Promise in Hong Kong (Sino Promise High Tech Holdings Limited), also revised on January 4, 2021:
UK:
upload_2021-8-13_13-35-14.png



Vive la différence!
 

MattKing

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grat

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Anecdotally, I have a 500ml bottle of Ilfosol 3 I opened in October 2020 that is still developing film. But I portioned it out into 5 100ml bottles, with practically no air in them, don't agitate them at all (the box has not moved in that time), and use approximately 50ml per developing cycle.

Ilfosol 3 has a terrible reputation for shelf-life when opened, so if I can get 10 months out of it, surely carefully managed HC-110, even the new stuff, should last well into the next decade.
 

YoIaMoNwater

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Every one of those ads is using the same image, from a bottle with a best before date in 2018 :D.
They, like your bottle, have the old, pre July 30, 2019 Catalog number of 5010541. Since July 2019 the Catalog number is 1058692.
What is the best before date on your bottle? Where does it say it was made?
Here is what the current as of late 2019, Made in the USA version looks like:
1564414830_1493206.jpg
Mine expires in 2022 and was made in 2019.

Matt I think you need to pay more attention on the images before making all these assumptions when you live on a different continent.

83A703FB-0EE4-447C-A120-212CD325B0BC.jpeg 92625C20-AC1E-4B8F-B175-B8045DB48724.jpeg ADAC437F-C08B-4F2E-B252-BFB0AAC94E13.jpeg 3C9E6932-D1CC-4127-8349-3F8CC5B7D5D7.jpeg BFBE2854-BE42-482A-9CB3-BEB48FC97E6D.jpeg
 

MattKing

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You are fortunate - that is one of the last bottles of the old, Made in Germany stuff.
If they have more you should buy it, because people all around the world - including in the UK/EU are looking for it!
EDIT: For clarity, your bottle is identical to the ones we had here before the big changes.
 
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Lachlan Young

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The novelty of the ingredients in the original cited patent were the various ammonia-based adducts (sulfite, bromide…) and the infamous PVP which people assume gave HC-110 an extra-low fog property that made it useful for developing old film. However has any commercially available version of HC-110 actually contained PVP? I don’t know.

From my reading of the Henn/ Surash patent, the PVP was there to suppress dichroic staining - I think the seeming novelty of the ingredients of HC-110 has caused people to ignore that the developers it was invented to replace are pretty low fog too - and the high activity of the developer/ low solvency + bromide restrainer are going to deliver lower fog than D-76 etc.
 
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Lachlan Young

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Any possibility of HC-110 being available in tablet form like the newly announced Tetenal Parvofin tablet developer?

Why? You might as well make up a PQ variant of DK-50 or DK-60a and compress that into tablet form with suitable encapsulation. HC-110 existed more to resolve industrial needs than those of amateur photographers with extremely low developer usage, and every aspect of its invention relied on sufficiently large scale use which could allow for investing in/ inventing a significantly more complicated manufacturing procedure.
 
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I assume most users of HC-110 today are amateurs and don't care about technological innovations behind the product. I could be wrong assuming this but as long as the developer retains its salient properties including long shelf-life, today's users wouldn't mind getting HC-110 in tablet form. How convenient it would be if one can get dilution B by using two tablets and dilution H by using one tablet!
 

Nicholas Lindan

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... today's users wouldn't mind getting HC-110 in tablet form ...

Kodak used to sell "Universal M-Q Developer" in tablets. Later they supplied it in two small packets in a sort of oversized matchbook. I guess Metol doesn't play well with others.
 
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